CA1325991C - Controlling hydrogen sulfide content in fuel oil distillation - Google Patents
Controlling hydrogen sulfide content in fuel oil distillationInfo
- Publication number
- CA1325991C CA1325991C CA000598298A CA598298A CA1325991C CA 1325991 C CA1325991 C CA 1325991C CA 000598298 A CA000598298 A CA 000598298A CA 598298 A CA598298 A CA 598298A CA 1325991 C CA1325991 C CA 1325991C
- Authority
- CA
- Canada
- Prior art keywords
- fuel oil
- fuel
- choline
- ppm
- oils
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
- C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
- C10L1/2225—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates hydroxy containing
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/20—Organic compounds not containing metal atoms
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G7/00—Distillation of hydrocarbon oils
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
ABSTRACT
The hydrogen sulfide content of the atmosphere over sour heavy fuels oils is controlled by the addition of choline to the fuel oil.
The hydrogen sulfide content of the atmosphere over sour heavy fuels oils is controlled by the addition of choline to the fuel oil.
Description
~ 3 2 5 9 9 The present invention pertains to a method for controlling the concentration or amount of H2S in the atmosphere of sour heavy fuel oils derived from petroleum and to maintain the specification of such oils with respect to Petroleum based heavy fuels are typically produced by the thermal distillation of crude petroleum in apparatus referred to as, crude oil distillation towers. Distillates from such towers include gas, gasoline, naphtha, kerosene, -~
gas oil, and diesel oil. The residue or bottoms from the distillation can either be coked in delayed coking drums at temperatures between 900 to 930F. to produce coke and distilled overhead products or can be shipped and sold -;~-directly to be used as fuel in boilers on ships or in power or steam plants.
Industrial fuel oils can also consist of one or more of the following products derived from petroleum: vacuum tower bottoms, catalytically cracked light or heavy gas oils and ~
catalytically cracked clarified oil. A No. 6 fuel oil is an ~ -example of such a product. It will-typically have a boiling --point of 660F., a specific gravity greater than 1.0 and 45 pour point. These products can contain significant amounts - -~
of H2S.
1 3259q 1 When "sour" crude oils, i.e., those containing sulfur-containing components, are distilled, such components distribute into both the various distillation products and also to the residue or bottoms in the distillation unit. In the ;
~.
'.~-.
~ "
;'"~'.
. .
':.''-.
~5 - la -~
1~59~1 overhead or distillate products, the sulfur components of the crude oil contain mercaptan6, thiols and organotlsulfldes, but little if any H2S. Numerous proposals have been made to "sweeten" such sour distlllate products by treatment w$th a variety of additives. Disclosures lllustratlve of these are contained in V.S. patents 2,671~048 lssued 2 March 1954 (addltlon of phenylenedlamlne together with an organlc base compound);
4,430,196 is6ued 2 February 1984 (addition of ~ -dimethylaminoethanol and/or dimethylisopropanolamine to the crude oil or the refinery stream products), ant 4,594,147 lssued 10 June 1986 (treating sour gasollne with choline).
None of the above proposals deal with the problem of H2S ln the atmosphere above or assoclated witb sour heavy fuel oils.
When such oils are to be used as fuel in industrial boilers or in electric utility steam plants or elsewhere, the presence of large amounts of H2S in the atmosphere above or associated with the oil during transit in barges or ships, or in~storage in refinery tanks or user tanks, constitutes a hazard to personnel who are in -~
the vicinity of ~he storage or transport facillties. Typically, 20 the H2S specification for such fuel oils~ls 100 ppm~r less. -~
Since some of such oils may contain up to 5,000 ppm of H2S, there is a need for an efficacious and economical method for reduclng :-the H2S concentratlon in the sour fuel oil atmosph:ere without affecting the burning propertles of the fuel.
~eu~ Y~u~ }~U~R~
The invention concerns a methot for maintaining the ~2S
content of the atmosphere above or associated with sour heavy ~. ..
fuel olls derived from petroleum sources wlthin~acceptable limit6 to avoid health hazards to personnel. This method~comprises treatlng such fuel 0118 with an effective amount of choline base.
The treatment is performed by adding~an approprlate amount of choline base to such oils or to tbe vapor~above them and heating ~ -the mixture to a temperature below the decomposltlon temperature of choline for a time sufficlent to reduce the H2S content of the 35 fuel oil atmosphere to acceptable~-or specification ~rade levels; :~
under lO0 ppm H2S is a typical specification. Tbls is ' - ' ;'~ -. .
'` 1 3259ql accomplished without impairing the burning characteristics or properties of ths fuel oil.
The invention comprises the discovery that choline base can be added to sour heavy fuel oils derived from petroleum in amounts e~fective to control the level or concentration of H2S in the atmosphere above or associated with such oils. ~-This results in reducing the H2S content of such atmospheres from as high as 5000 ppm, and often within the range of 120 to 4500 ppm, down to 100 ppm or less which satisfies a typical specification for such fuels. Such treatment does not impair the fuel burning characteristics or properties of -such fuel oils. -..
Choline is described in Merck Index, 10th Edition, Merck & Co. (1983) and in the J. Org. Chem., Vol. 41, No. 23,3373 (1976~. It is typically represented as Me3N-CH2CH2-OH. The term choline as used herein and in the appended claims also includes derivatives of choline represented as Me3N-CH2CH2-O~OR where R = alkyl (C1 to C20).
The amount of choline base added to the sour heavy fuel ~ -oil is directly proportional to the amount of H2S present in -the atmosphere above or associated with the fuel oil. The choline base is mixed with and dissolved in the oil and then 1 325991 ;~
the choline-containing oil is maintained at ambient temperature but is preferably heated within the temperature range of 100~ to 225F., for a time until the H2S in the fuel oil atmosphere is reduced to an acceptable or specification ;
grade level. A preferred procedure is to heat the choline-containing fuel oil at a temperature of 180-F for 2 hours. -~
The temperature should be below the decomposition temperature -~
of the choline base or choline derivative. When choline base itself is used, the heating temperature of the choline- ~ -containing oil should be below 230-F.
'' 'i" ', i ' The amount of choline to be used and/or the heat treatment time employed can readily be determin-d by those -skilled in the art by periodically or routinely analyzing the -- . -. ,::
fuel oil a~mosphere for H2S.
~'' ';, ':",' ~'.;."
,, .... :, .. .
~5 '"' ~
- 3a - ~ ~
.,:
..
1 325991 ~
The following examples illustrate preferred procedures for performing the method of the invention.
Three samples (A, B and C) of sour heavy marine fuel oil and one sample of low H2S fuel oil ~D) were obtained from a gulf coast oll refinery. These had specific gravity numbers above 1.0 and a~mospheric H2S contents or values as follows:
Fuel Oil Sample H2S ppm :.
D* 3000*
*Controlled amount of H2S added to oil -,:
Samples of the above fuel oils were mixed with varying amount~ of choline base and heated for 2 hours at 180F ln a clo~ed vessel, after which the atmosphere in the vessel was -analyzed foT H2S using the Drager method.
.
Fuel Oil ppm Example No. Sample Choline H2S ppm 2 A 1000 25 ~ :
gas oil, and diesel oil. The residue or bottoms from the distillation can either be coked in delayed coking drums at temperatures between 900 to 930F. to produce coke and distilled overhead products or can be shipped and sold -;~-directly to be used as fuel in boilers on ships or in power or steam plants.
Industrial fuel oils can also consist of one or more of the following products derived from petroleum: vacuum tower bottoms, catalytically cracked light or heavy gas oils and ~
catalytically cracked clarified oil. A No. 6 fuel oil is an ~ -example of such a product. It will-typically have a boiling --point of 660F., a specific gravity greater than 1.0 and 45 pour point. These products can contain significant amounts - -~
of H2S.
1 3259q 1 When "sour" crude oils, i.e., those containing sulfur-containing components, are distilled, such components distribute into both the various distillation products and also to the residue or bottoms in the distillation unit. In the ;
~.
'.~-.
~ "
;'"~'.
. .
':.''-.
~5 - la -~
1~59~1 overhead or distillate products, the sulfur components of the crude oil contain mercaptan6, thiols and organotlsulfldes, but little if any H2S. Numerous proposals have been made to "sweeten" such sour distlllate products by treatment w$th a variety of additives. Disclosures lllustratlve of these are contained in V.S. patents 2,671~048 lssued 2 March 1954 (addltlon of phenylenedlamlne together with an organlc base compound);
4,430,196 is6ued 2 February 1984 (addition of ~ -dimethylaminoethanol and/or dimethylisopropanolamine to the crude oil or the refinery stream products), ant 4,594,147 lssued 10 June 1986 (treating sour gasollne with choline).
None of the above proposals deal with the problem of H2S ln the atmosphere above or assoclated witb sour heavy fuel oils.
When such oils are to be used as fuel in industrial boilers or in electric utility steam plants or elsewhere, the presence of large amounts of H2S in the atmosphere above or associated with the oil during transit in barges or ships, or in~storage in refinery tanks or user tanks, constitutes a hazard to personnel who are in -~
the vicinity of ~he storage or transport facillties. Typically, 20 the H2S specification for such fuel oils~ls 100 ppm~r less. -~
Since some of such oils may contain up to 5,000 ppm of H2S, there is a need for an efficacious and economical method for reduclng :-the H2S concentratlon in the sour fuel oil atmosph:ere without affecting the burning propertles of the fuel.
~eu~ Y~u~ }~U~R~
The invention concerns a methot for maintaining the ~2S
content of the atmosphere above or associated with sour heavy ~. ..
fuel olls derived from petroleum sources wlthin~acceptable limit6 to avoid health hazards to personnel. This method~comprises treatlng such fuel 0118 with an effective amount of choline base.
The treatment is performed by adding~an approprlate amount of choline base to such oils or to tbe vapor~above them and heating ~ -the mixture to a temperature below the decomposltlon temperature of choline for a time sufficlent to reduce the H2S content of the 35 fuel oil atmosphere to acceptable~-or specification ~rade levels; :~
under lO0 ppm H2S is a typical specification. Tbls is ' - ' ;'~ -. .
'` 1 3259ql accomplished without impairing the burning characteristics or properties of ths fuel oil.
The invention comprises the discovery that choline base can be added to sour heavy fuel oils derived from petroleum in amounts e~fective to control the level or concentration of H2S in the atmosphere above or associated with such oils. ~-This results in reducing the H2S content of such atmospheres from as high as 5000 ppm, and often within the range of 120 to 4500 ppm, down to 100 ppm or less which satisfies a typical specification for such fuels. Such treatment does not impair the fuel burning characteristics or properties of -such fuel oils. -..
Choline is described in Merck Index, 10th Edition, Merck & Co. (1983) and in the J. Org. Chem., Vol. 41, No. 23,3373 (1976~. It is typically represented as Me3N-CH2CH2-OH. The term choline as used herein and in the appended claims also includes derivatives of choline represented as Me3N-CH2CH2-O~OR where R = alkyl (C1 to C20).
The amount of choline base added to the sour heavy fuel ~ -oil is directly proportional to the amount of H2S present in -the atmosphere above or associated with the fuel oil. The choline base is mixed with and dissolved in the oil and then 1 325991 ;~
the choline-containing oil is maintained at ambient temperature but is preferably heated within the temperature range of 100~ to 225F., for a time until the H2S in the fuel oil atmosphere is reduced to an acceptable or specification ;
grade level. A preferred procedure is to heat the choline-containing fuel oil at a temperature of 180-F for 2 hours. -~
The temperature should be below the decomposition temperature -~
of the choline base or choline derivative. When choline base itself is used, the heating temperature of the choline- ~ -containing oil should be below 230-F.
'' 'i" ', i ' The amount of choline to be used and/or the heat treatment time employed can readily be determin-d by those -skilled in the art by periodically or routinely analyzing the -- . -. ,::
fuel oil a~mosphere for H2S.
~'' ';, ':",' ~'.;."
,, .... :, .. .
~5 '"' ~
- 3a - ~ ~
.,:
..
1 325991 ~
The following examples illustrate preferred procedures for performing the method of the invention.
Three samples (A, B and C) of sour heavy marine fuel oil and one sample of low H2S fuel oil ~D) were obtained from a gulf coast oll refinery. These had specific gravity numbers above 1.0 and a~mospheric H2S contents or values as follows:
Fuel Oil Sample H2S ppm :.
D* 3000*
*Controlled amount of H2S added to oil -,:
Samples of the above fuel oils were mixed with varying amount~ of choline base and heated for 2 hours at 180F ln a clo~ed vessel, after which the atmosphere in the vessel was -analyzed foT H2S using the Drager method.
.
Fuel Oil ppm Example No. Sample Choline H2S ppm 2 A 1000 25 ~ :
4 B 1000 O -~
C 500 ~250 ~ :
6 C 1000 90 :
The above data show that the amount of choline base to be used dPpend~ on the amount of H2S present in the sour fuel oil atmo~phere and may be used as guidelines for choline additioD to fuel oils havlng a wide range of at spheric ~2S.
,'
C 500 ~250 ~ :
6 C 1000 90 :
The above data show that the amount of choline base to be used dPpend~ on the amount of H2S present in the sour fuel oil atmo~phere and may be used as guidelines for choline additioD to fuel oils havlng a wide range of at spheric ~2S.
,'
Claims (7)
1. The method of maintaining the H2S content of the atmosphere above heavy sour fuel oils within acceptable limits which comprises treating such fuel oils with an effective amount of choline base at a temperature below the decomposition temperature of choline base.
2. The method according to claim 1 wherein the amount of choline used to treat the fuel oil is directly proportional to the amount of H2S present in the atmosphere above the fuel oil.
3. The method according to claim 1 wherein the treating temperature is between ambient and 225°F.
4. The method according to claim 1 where the treating temperature is about 180°F.
5. The method according to claim 1 wherein the fuel oil atmosphere contains up to 5000 ppm of H2S.
6. The method according to claim 3 wherein the fuel oil atmosphere contains up to 5000 ppm of H2S.
7. The method of claim 4 wherein the fuel oil atmosphere contains up to 5000 ppm of H2S.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/217,539 US4867865A (en) | 1988-07-11 | 1988-07-11 | Controlling H2 S in fuel oils |
| US217,539 | 1988-07-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1325991C true CA1325991C (en) | 1994-01-11 |
Family
ID=22811488
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000598298A Expired - Fee Related CA1325991C (en) | 1988-07-11 | 1989-05-01 | Controlling hydrogen sulfide content in fuel oil distillation |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4867865A (en) |
| EP (1) | EP0400095A4 (en) |
| JP (1) | JPH03501270A (en) |
| CA (1) | CA1325991C (en) |
| WO (1) | WO1990000588A1 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5183560A (en) * | 1991-09-09 | 1993-02-02 | Baker Hughes Incorporated | Treatment of oils using choline base |
| US5190640A (en) * | 1991-09-18 | 1993-03-02 | Baker Hughes Incorporated | Treatment of oils using aminocarbinols |
| AU2714192A (en) * | 1991-10-21 | 1993-04-22 | Baker Hughes Incorporated | Treatment of oils using epoxylated tertiary amines |
| US5213680A (en) * | 1991-12-20 | 1993-05-25 | Baker Hughes Incorporated | Sweetening of oils using hexamethylenetetramine |
| CA2133270C (en) * | 1994-03-03 | 1999-07-20 | Jerry J. Weers | Quaternary ammonium hydroxides as mercaptan scavengers |
| PT1298185E (en) * | 2001-09-27 | 2005-08-31 | Kurita Europ Gmbh | METHOD TO PREVENT INCRUSTACTIONS AND CORROSION CAUSED BY AMMONIUM CHLORIDE |
| US20080230445A1 (en) | 2007-03-19 | 2008-09-25 | Baker Hughes Incorporated | Method of scavenging mercaptans from hydrocarbons |
| US8679203B2 (en) * | 2007-03-19 | 2014-03-25 | Baker Hughes Incorporated | Method of scavenging mercaptans from hydrocarbons |
| US8048175B2 (en) | 2008-04-11 | 2011-11-01 | Baker Hughes Incorporated | Quick removal of mercaptans from hydrocarbons |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2671048A (en) * | 1951-03-01 | 1954-03-02 | Universal Oil Prod Co | Treatment of hydrocarbon distillates |
| US3159570A (en) * | 1962-12-19 | 1964-12-01 | Charles O Petty | Hydrazine sweetening |
| US3372009A (en) * | 1964-06-18 | 1968-03-05 | Mobil Oil Corp | Liquid fuel compositions containing as anti-corrosion agent an alkyl monoalkanol amino compound |
| US4412913A (en) * | 1982-08-05 | 1983-11-01 | Standard Oil Company (Indiana) | Use of alkanolamines in sweetening sour liquid hydrocarbon streams |
| US4430196A (en) * | 1983-03-28 | 1984-02-07 | Betz Laboratories, Inc. | Method and composition for neutralizing acidic components in petroleum refining units |
| US4600518A (en) * | 1985-07-15 | 1986-07-15 | Nalco Chemical Company | Choline for neutralizing naphthenic acid in fuel and lubricating oils |
| US4594147A (en) * | 1985-12-16 | 1986-06-10 | Nalco Chemical Company | Choline as a fuel sweetener and sulfur antagonist |
-
1988
- 1988-07-11 US US07/217,539 patent/US4867865A/en not_active Expired - Fee Related
-
1989
- 1989-04-12 WO PCT/US1989/001524 patent/WO1990000588A1/en not_active Application Discontinuation
- 1989-04-12 JP JP1504788A patent/JPH03501270A/en active Pending
- 1989-04-12 EP EP19890904949 patent/EP0400095A4/en not_active Withdrawn
- 1989-05-01 CA CA000598298A patent/CA1325991C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| EP0400095A1 (en) | 1990-12-05 |
| US4867865A (en) | 1989-09-19 |
| JPH03501270A (en) | 1991-03-22 |
| WO1990000588A1 (en) | 1990-01-25 |
| EP0400095A4 (en) | 1991-03-13 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed |